Use of novel ethers as oxydimethylating agents

ABSTRACT

A compound having the formula 
     
         R -- SO.sub.2 O -- CH.sub.2 -- O -- CH.sub.2 -- OSO.sub.2 -- R 
    
     wherein R is alkyl, is prepared by reacting a compound having the formula ##STR1## wherein R and R&#39; are alkyl with a cyclic polyoxymethylene or a linear polyoxymethylene in a substantially humidity-free environment. The compound is useful as an oxydimethylating agent for organic compounds.

This is a division of application Ser. No. 597,950, filed July 21, 1975.now U.S. Pat. No. 4,025,542 granted 5/24/77.

This invention relates to a novel ether, a novel method of preparingsaid ether and the use of the ether as an oxydimethylating agent fororganic compounds.

There are several compounds which are known in the art to be useful asalkoxyalkylating agents. These agents are compounds which can be reactedwith various compounds such as mercaptans, amines, aromatichydrocarbons, phenols and the like containing reactive groups such ashydrogen to replace the reactive group with alkoxyalkyl groups.

Thus, for example, the reaction product of dimethoxymethane with acetylmethanesulfonate is described in M. H. Karger and Y. Mazur, J. Am. Chem.Soc., 91, 5663 (1969). The resulting compound, methoxymethylmethanesulfonate, described in this reference is useful inmethoxymethylating various compounds containing reactive groups.

The reactivity of methoxymethyl methanesulfonate is of a very highorder, being reported by Karger and Mazur to be about 10⁴ times asreactive as the corresponding chloride and acetate. Althoughbifunctional analogs of the methanesulfonate until now have beenunknown, they are of great potential interest, not only for thepreparation of simple organic compounds but also in the preparation ofpolymers.

Attempts to prepare bis-sulfonates of the type described herein byvarious existing methods have not been successful. For example, theattempted formation of bis(p-toluenesulfonoxymethyl) ether by reactionof silver p-toluenesulfonate) with a bis(halomethyl) ether led only tothe p-toluenesulfonic anhydride. Furthermore, the reaction ofmethanesulfonyl chloride or methanesulfonic anhydride with trioxanefailed to produce the dimesylate described hereinafter.

The objects of this invention are to provide (1) bifunctional compoundshaving great reactivity, (2) a method of preparing such compounds and(3) substances useful in the preparation of polymers, photographichardening agents and the like. An example of their utility in hardenersynthesis is their reaction with 2-mercaptoethanol to form5-oxa-3,7-dithianonane-1,9-diol, a material described in U.S. Pat. No.3,539,644 to Burness et al.

In accordance with the present invention, it has been found that a novelbis(organosulfonoxymethyl) ether can be prepared which can be used as anoxydimethylating agent for compounds containing reactive groups.

In one embodiment this invention comprises a compound having the formulaR -- SO₂ O -- CH₂ -- O -- CH₂ -- OSO₂ -- R wherein R is alkyl.

In another embodiment this invention comprises a novel method ofpreparation of bis(alkylsulfonoxymethyl) ether comprising reacting acompound having the formula ##STR2## wherein R and R' are alkyl with acyclic or linear polyoxymethylene at a temperature range of 0° C toabout 120° C in a substantially moisture-free atmosphere.

In still another embodiment a compound having the formula

    R -- SO.sub.2 O -- CH.sub.2 -- O -- CH.sub.2 -- OSO.sub.2 -- R

wherein R is alkyl is used as an oxydimethylating agent for compoundscontaining reactive groups.

The novel bis(alkylsulfonoxymethyl) ether of this invention has theformula

    R -- SO.sub.2 O -- CH.sub.2 -- O -- CH.sub.2 -- OSO.sub.2 -- R

wherein R is alkyl preferably containing from 1 to 6 carbon atoms, andmore preferably from 1 to 4 carbon atoms such as methyl, ethyl, propyl,butyl, and isomers thereof. The most preferred compound is that whereinR is methyl.

The above novel compounds are prepared by reacting a compound having theformula ##STR3## wherein R is as described above and R' is alkyl,preferably containing from 1 to 4 carbon atoms, with an ether selectedfrom the group consisting of cyclic polyoxymethylenes such as trioxaneand tetraoxane and linear polyoxymethylenes such as trioxymethylenediacetate, tetraoxymethylene diacetate, pentaoxymethylene diacetate andhexaoxymethylene diacetate having the formula

    CH.sub.3 CO.sub.2 (CH.sub.2 O).sub.n COCH.sub.3

wherein n is an integer preferably from 3 to 6.

The molar ratio of compounds having the formula ##STR4## such as acetylmethanesulfonate to the cyclic or linear polyoxymethylene is generallyaround 2:1 but can vary widely.

The reaction temperatures can vary with time of reaction. A temperatureof 0° C to about 120° C may be used; generally longer reaction timessuch as greater than 100 hours are useful at 0° C and shorter times arenecessary at higher temperatures such as less than one-half hour at 100°C.

Although it is preferred to run the reaction neat, some solvents whichdo not react with either of the reactants may be used.

The reaction must be carried out in a substantially moisture-freeenvironment to avoid side reactions with both the acetyl mesylatereactant and the product. In this respect, the environment preferablycontains no moisture.

The novel bis(alkylsulfonoxymethyl) ether of this invention can be usedas a reactant to oxydimethylate a variety of compounds generally of twoclasses: Class A, active hydrogen compounds preferably in the form oftheir alkaline metal or similar salt-like forms, such as alcohols,phenols, mercaptans, imides and active methylene compounds and B basiccompounds such as are generally capable of salt formation withalkylating agents including teritiary amines, phosphines, thioethers,thiourea, amine oxides and numerous heterocyclic compounds.

Examples of compounds containing the above reactive groups includeethanol, n-butanol, chlorophenol, nitrophenol, naphthol, n-butanethiol,2-mercaptoethanol, thiophenol, 2-mercaptoethyl acetate, α-toluenethiol,benzothiazole-2-thiol, phthalimide, diethyl malonate, ethylacetoacetate, and the like, as well as basic compounds such as pyridine,quinoline, N-methylmorpholine, N-methylimidazole, tributylphosphine,thiolane, thiourea and pyridine-N-oxide.

Solvents useful for these reactions are generally limited due to theextreme reactivity of the dimesylate. For type A reactionstetrahydrofuran, dioxane or acetonitrile are useful and for type Breactions cyclic ethers, acetonitrile, and chlorinated solvents can beused.

Typical oxydimethylating reactions are as follows: ##STR5##

The compounds of this invention are particularly useful inoxydimethylating sodium 2-hydroxyethylmercaptide to obtainbis(vinylsulfonylmethyl) ether as described in U.S. Pat. No. 3,539,644.The oxydimethylated product is highly useful in forming hardeners forgelatino photographic materials.

The oxydimethylation reaction can be carried out, if desired, in asolvent such as cyclic ethers such as tetrahydrofuran or dioxane oracetonitrile at temperatures from 0° C to about 100° C and preferablyfrom about 0° C to about 40° C.

The following examples are included for a further understanding of theinvention.

EXAMPLE 1 ##STR6##

Acetyl methanesulfonate [13.8 g, 0.1 M, prepared by the proceduredescribed in J. Org, Chem., 36, 528 (1971)] was cooled to 5° C and 4.5 g(0.05 M) of s-trioxane was added. The mixture was stirred at 5° C for0.5 hr. and allowed to warm gradually to 25° C. It was then heated at80° C for 0.5 hr. and the volatiles stripped at reduced pressure.Distillation yielded 6.5 g. (60%) of bis(methanesulfonoxymethyl)ether;b.p. 122° C (pot temp.) at 7μ; m.p. 52°-53° C. Identity was establishedby the nmr spectrum and elementary analysis.

Anal. Calc'd. for C₄ H₁₀ O₇ S₂ : C, 20.4; H, 4.6; S, 27.4. Found: C,20.3; H, 4.9; S, 27.3.

EXAMPLE 2

The acetyl methanesulfonate (285.2 g, 2.06 mole) of Example 1 wastransferred by syringe to a dry-nitrogen filled flask fitted with athermometer, magnetic stirring bar, glass adapter for nitrogen inlet andvacuum take-off. The mixed anhydride was cooled to -5° C and 92.9 g(1.03 mole) of s-trioxane was added over a 10-minute period withstirring. When the solution was complete (20 minutes), the well-stirredreaction mixture was heated to 90° C with a 0.5 mm vacuum applied whenthe temperature reached 35° C. Heating, with stirring, under vacuum wascontinued for 24 hours during which time 118.5 g (90%) of methylenediacetate was collected in a cold trap. The dark brown reaction mixturewas cooled to room temperature, brought to atmospheric pressure with drynitrogen, dissolved in 120 ml of dry tetrahydrofuran at roomtemperature, treated with carbon, and filtered. An additional 80 ml ofdry tetrahydrofuran was used as wash solvent. The light- to medium-brownfiltrate was seeded and cooled to -35° C for crystallization. Thecrystalline mass was broken up several times during the cold period toencourage further crystallization. The product was collected by suctionfiltration under dry nitrogen in a glove box, washed with cold, drytetrahydrofuran, then with ethyl ether and dried in the funnel bydrawing dry nitrogen through the funnel. A yield of 168.4 g (70%) wasobtained. The bis(methanesulfonoxymethyl)ether was off-white to tan incolor with a melting point in the range 52°-58° C.

EXAMPLE 3

Using the procedure of Example 2, acetyl methanesulfonate and tetroxane,in a molar ratio of 2:1, were reacted for 18-24 hours at 90° C and 0.5mm. pressure allowing the bis(acetoxymethyl)ether to distill. Theresidual oil was recrystallized from a small volume of drytetrahydrofuran to give a 67% yield of

    CH.sub.3 SO.sub.3 CH.sub.2 OCH.sub.2 OSO.sub.2 CH.sub.3

example 4

a mixture of 12.7 g of acetyl methanesulfonate and 9.15 g oftrioxymethylene diacetate was prepared at 0° C and then stirred at 25° Cfor 20 hours. Distillation at 10μ produced 4.5 g of CH₃ SO₃ CH₂ OCH₂OSO₂ CH₃ b.p. 110°-115° C (pot temp.); m.p. 57°-59° C.

EXAMPLE 5 Oxydimethylation of mercaptoethanol

To a 50 ml solution of anhydrous isopropyl alcohol, containing 0.41 g(0.017 M) of sodium hydride (ether washed), was added 1.33 g (0.017 M)of 2-mercaptoethanol. The resulting suspension was stirred at 25° C for15 minutes until a homogeneous solution was formed. A dioxane solutionunder N₂ atmosphere, containing 1.97 g (0.0084 M) ofbis(methanesulfonoxymethyl)ether was then added dropwise over a10-minute period. The reaction mixture was stirred for 1 hour at whichtime the insoluble materials formed were filtered off. The filtrate wasconcentrated to dryness and the resulting residue extracted with ethylacetate. The extracts were evaporated to give 1.5 g (91%) of5-oxa-3,7-dithianonane-1,9-diol, the nmr of which corresponded to thatprepared from bis(chloromethyl)ether (see U.S. Pat. No. 3,539,644).

EXAMPLE 6

The procedure of Example 5 was repeated with the exception thatn-butanethiol was the material oxydimethylated. The resulting productwas an 85% yield of bis(butylthiomethyl)ether.

Example 7 Oxydimethylation of N-methylmorpholine

To a solution of N-methylmorpholine in acetonitrile was added a0.5-molar equivalent of crude CH₃ SO₃ CH₂ OCH₂ OSO₂ CH₃. The oil whichseparated was added, in turn, to an aqueous solution of sodiumperchlorate to produce a colorless, crystalline solid, the nmr spectrumof which confirmed the structure to beN,N'-oxydimethyl-bis(N-methylmorpholinium perchlorate).

EXAMPLE 8 Oxybis(N-methylpyridinium methanesulfonate)

A solution of a bis(methanesulfonoxymethyl)ether in 20 ml of dryacetonitrile was added dropwise to a stirred solution of 5.9 g ofpyridine in 40 ml of dry acetonitrile at 25° C. The crude product beganto separate almost immediately. The reaction mixture was stirred for anhour at 25° C, cooled and filtered. The crude product was recrystallizedonce from methanol to yield 11.7 g of the colorless crystalline saltproduct having a melting point of 184.5 to 186.5° C.

EXAMPLE 9 Bis(n-butoxymethyl)ether

To a solution of 0.05 mole of sodium n-butoxide and 50 ml dry n-butanolwas added a solution of 0.025 mole of bis(methanesulfonoxymethyl)etherin 10 ml of dry acetonitrile at 25° C. The reaction mixture was stirredfor one hour at 25° C and filtered. The product achieved wasbis(n-butoxymethyl)ether.

EXAMPLE 10 Bis(ethanesulfonoxymethyl)ether

A sample of 64.0 g of acetyl ethanesulfonate was cooled to -10° C underdry nitrogen and 18.9 g of trioxane was added with stirring over a 15min. period with the temperature kept below -5° C. When all of thetrioxane had dissolved, the solution was allowed to warm to 10° C and avacuum of 0.5 mm was applied. The reaction was stirred under vacuum for18 hrs. at 80° C, cooled to room temperature and the crude productextracted with four 50 ml portions of dry ethyl ether under nitrogen ina glove box. The residue was distilled to give colorlessbis(ethanesulfonoxymethyl)ether boiling at 120°-123° C (8μ), and havinga refractive index n_(D) ²⁴ 1.4551.

This invention has been described in detail with particular reference tocertain embodiments thereof, but it will be understood that variationsand modifications can be effected within the spirit and scope of theinvention.

What is claimed is:
 1. In the method of oxydimethylating an organiccompound with an oxydimethylating agent the improvement comprisingreacting said organic compound with an oxydimethylating agent having theformula

    R -- SO.sub.2 O -- CH.sub.2 -- O -- CH.sub.2 -- OSO.sub.2 -- R

wherein R is alkyl having from 1 to 6 carbon atoms.
 2. The method ofclaim 1 wherein the organic compound contains a reactive hydrogen atom.3. The method of claim 1 wherein R is methyl.
 4. The method of claim 1wherein said organic compound is 2-mercaptoethanol and saidoxydimethylating agent is bis(methanesulfonoxymethyl) ether.